EP0171225B1 - Adhésif sensible à la pression et copolymères pour le préparer - Google Patents

Adhésif sensible à la pression et copolymères pour le préparer Download PDF

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Publication number
EP0171225B1
EP0171225B1 EP85305240A EP85305240A EP0171225B1 EP 0171225 B1 EP0171225 B1 EP 0171225B1 EP 85305240 A EP85305240 A EP 85305240A EP 85305240 A EP85305240 A EP 85305240A EP 0171225 B1 EP0171225 B1 EP 0171225B1
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weight
block
block copolymer
aromatic compound
alkenyl aromatic
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EP85305240A
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German (de)
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EP0171225A1 (fr
Inventor
Akira Iio
Kunihiko Muramori
Mikio Takeuchi
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JSR Corp
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Shell Internationale Research Maatschappij BV
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C08F297/046—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes polymerising vinyl aromatic monomers and isoprene, optionally with other conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/021—Block or graft polymers containing only sequences of polymers of C08C or C08F
    • C08G81/022—Block or graft polymers containing only sequences of polymers of C08C or C08F containing sequences of polymers of conjugated dienes and of polymers of alkenyl aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

Definitions

  • This invention relates to a straight and/or branched chain, alkenyl aromatic compound-conjugated diene block copolymer coupled with a tin-based coupling agent and suitable for use in pressure-sensitive adhesives. It also provides a pressure-sensitive adhesive composition containing said coupled block copolymer. More particularly, this invention relates to a coupled block copolymer having (1) non-elastomeric blocks of an alkenyl aromatic compound polymer and (2) elastomeric blocks of a conjugated diene polymer or of a copolymer of a conjugated diene (main component) and an alkenyl aromatic compound, both being coupled with a tin-type coupling agent, and particularly suitable for use in hot-melt type pressure-sensitive adhesives.
  • thermoplastic elastomer having excellent adhesion-holdability, peeling strength and die-cuttability.
  • Block copolymers produced according to known processes for use in pressure-sensitive adhesives are highly likely to undergo "blocking" during storage and form large lumps, and, accordingly, their handling in the production of a pressure-sensitive adhesive therefrom is difficult.
  • anti-blocking agents such as inorganic compounds (e.g. talc, calcium carbonate) or metallic soaps (e.g., sodium stearate, calcium stearate) have often been added to these block copolymers.
  • inorganic compounds e.g. talc, calcium carbonate
  • metallic soaps e.g., sodium stearate, calcium stearate
  • pressure-sensitive adhesives produced from a block copolymer containing a large amount of such an anti-blocking agent possess reduced adhesion characteristics, particularly adhesion-holdability and peeling strength.
  • a coupled alkenyl aromatic compound-conjugated diene block copolymer having a total bound alkenyl aromatic compound content of from 3 to 70% by weight, having a weight average molecular weight of from 10,000 to 1,000,000; and represented by the general formula: (1) [(A-B) m ] n X and/or (2) [(A-B-A') m ] n X wherein: A and A' are the same or different and each represents a block of an alkenyl aromatic compound polymer having a weight average molecular weight in the range of from 3,000 to 200,000; B represents a block of a conjugated diene polymer or a block of a conjugated diene-alkenyl aromatic compound copolymer having a proportion of conjugated diene of at least 50% by weight, said block having a weight average molecular weight in the range of from 7,000 to 700,000; X represents the residue of a tin-containing coupling agent or a mixture
  • the invention further provides an anti blocking, pressure-sensitive adhesive composition comprising:
  • X contains preferably from 20 to 100 mol% of the residue of a tin-containing coupling agent.
  • the coupled block copolymer of this invention is a coupled straight and/or branched chain block copolymer obtained by copolymerizing an alkenyl aromatic compound and a conjugated diene compound, further polymerizing an alkenyl aromatic compound, if necessary, and subjecting the resulting polymers to coupling with at least a tin-containing coupling agent.
  • the weight average molecular weight of the coupled block copolymer is more preferably from 50,000 to 700,000, and most preferably from 100,000 to 600,000. When the weight average molecular weight is less than 10,000, the pressure-sensitive adhesive composition of this invention has insufficient adhesion-holdability. When the weight average molecular weight exceeds 1,000,000, the composition has insufficient initial adhesive strength.
  • the weight average molecular weight of the block of the alkenyl aromatic compound polymer is suitably from 3,000 to 200,000, preferably from 4,000 to 150,000, more preferably from 5,000 to 100,000, most preferably from 5,000 to 50,000.
  • the weight average molecular weight of the block of the polymer of conjugated diene is suitably from 7,000 to 700,000, preferably from 10,000 to 500,000, more preferably from 10,000 to 300,000, most preferably from 10,000 to 200,000.
  • the content of the bound alkenyl aromatic compound component in the coupled block copolymer is from 3 to 70% by weight. This content is preferably from 5 to 50% by weight, more preferably from 5 to 40% by weight.
  • a pressure-sensitive adhesive composition produced from the coupled block copolymer has insufficient adhesion-holdability and die-cuttability.
  • the content exceeds 70% by weight, the composition has insufficient initial adhesive strength.
  • the die-cuttability mentioned above is the property demonstrated below.
  • a pressure-sensitive adhesive sheet is stuck to a release paper; the resulting laminate is subjected to a punching die so that only the pressure-sensitive adhesive sheet is punched out in the desired label shapes; then the unnecessary portion of the sheet is stripped from the release paper.
  • the die-cuttability is poor, the sheet adheres to the die and even those portions necessary as pressure-sensitive adhesive lables are stripped from the release paper, or, when the uncut part of the pressure-sensitive adhesive sheet is stripped from the release paper, the adhesive labels are also stripped.
  • the coupled block copolymer of this invention should contain at least 20% by weight of a tin compound-coupled alkenyl aromatic compound-conjugated diene block copolymer.
  • the content of the coupled block copolymer in the block copolymer mixture of this invention is preferably at least 25%, more preferably at least 30%. When the content is less than 20%, a pressure-sensitive adhesive composition produced from the block copolymer mixture has a poor balance between initial adhesive strength and adhesion-holdability and also undergoes blocking during storage.
  • the coupled alkenyl aromatic compound-conjugated diene block copolymer of this invention is characterized in that the alkenyl aromatic compound-conjugated diene block copolymers produced by polymerizing an alkenyl aromatic compound and a conjugated diene are coupled with (A) a tin type compound such as a tin chloride compound or (B) a mixture of said tin type compound and at least one non-tin type coupling agent added to the polymerization system after the polymerization.
  • a tin type compound such as a tin chloride compound
  • B a mixture of said tin type compound and at least one non-tin type coupling agent added to the polymerization system after the polymerization.
  • the coupled block copolymer of this invention produced using at least one tin-containing coupling agent as mentioned above is used as hot-melt type pressure-sensitive adhesives, the initial adhesive strength, adhesion-holdability, peeling strength and die-cuttability of said adhesives are remarkably improved, and these adhesives cause only limited blocking and are very easy to store and handle.
  • the coupled block copolymer of this invention firstly 10 to 100% by weight of the total amount of an alkenyl aromatic compound is polymerized. After the polymerization of said alkenyl aromatic compound has been substantially completed, a conjugated diene or a mixture consisting of 50% by weight or more of a conjugated diene and 50% by weight or less of an alkenyl aromatic compound is added and polymerized.
  • the conjugated diene or the mixture thereof can be added in one portion or in at least two portion, preferably in 2 to 10 portions and polymerized continuously or in plural stages.
  • the block copolymer thus produced has, as the B portion of the previously shown general formula 0 to 10 tapered blocks in which the content of bound alkenyl aromatic compound increases gradually.
  • the block copolymer preferably has 1 to 10, more preferably 2 to 8 tapered blocks.
  • the weight ratio [(2)/(1)] of the tin type coupling agent (1) and the non-tin type coupling agent (2) is preferably 0 - 5, more preferably 0 - 3.
  • the amount of the coupling agent added is 0.2 to 1.8 equivalents, preferably 0.4 to 1.5 equivalents, per equivalent of lithium of the lithium-terminated block copolymer.
  • the coupled block copolymer obtained contains too large an amount of uncoupled polymers and when it is used as a pressure-sensitive adhesive, adhesion-holdability becomes inferior.
  • the polymerization of an alkenyl aromatic compound or a conjugated diene be conducted in the presence of an ether or a tertiary amine.
  • the amount of the ether or the tertiary amine added is preferably 0.0005 to 1 part by weight, more preferably 0.005 to 0.5 part by weight per 100 parts by weight of the monomers. When the amount is outside this range, a pressure-sensitive adhesive produced from the resulting block copolymer is poor in balance between adhesive strength and adhesion-holdability.
  • the ether or the tertiary amine includes, for example, tetrahydrofuran, diethyl ether, anisole, dimethoxybenzene, ethylene glycol dimethyl ether, triethylamine, N-dimethylaniline, and pyridine.
  • the alkenyl aromatic compound used in this invention includes styrene, ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene, dimethylstyrene, and vinylnaphthalene. Of these, styrene is preferred.
  • the conjugated diene includes butadiene, isoprene, and piperylene. Of these, isoprene is preferred.
  • the block copolymer used in this invention can be produced according to an isothermal polymerization process or an adiabatic polymerization process.
  • the polymerization temperature is preferably 10 to 140 °C, more preferably 30 to 120 °C, and most preferably 30 to 110 °C.
  • a hydrocarbon solvent may be used.
  • this solvent include cyclopentane, cyclohexane, benzene, ethylbenzene, xylene and mixtures thereof with pentane, hexane, heptane, or butane.
  • the organolithium compound used as a polymerization initiator includes, for example, n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium, isohexyllithium, phenyllithium, and naphthyllithium. It is used in an amount of 0.01 to 1.0 part by weight per 100 parts by weight of the monomers.
  • a tin halide compound is preferred.
  • the tin halide compound includes tin halides such as stannous chloride, stannic chloride, stannous bromide, stannic bromide, stannous iodide, stannic iodide, stannous fluoride, stannic fluoride and alkyltin halides such as methyltin trichloride, butyltin trichloride and dibutyltin dichloride. Of these, stannic chloride, stannic bromide and butyltin trichloride are particularly preferred.
  • non-tin type coupling agent there may be used divinyl aromatic compounds such as divinylbenzene and divinylnaphthalene; dihalogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, dibromomethane, dichloropropane, and dibromopropane; trihalogenated alkanes such as chloroform, trichloroethane, trichloropropane, and tribromopropane; benzoic acid esters; halogenated silicon compounds such as silicon tetrachloride, dimethyldichlorosilicon, and tetrabromosilicon; carbon monoxide; 2-chloropropene; and 1-chloro-1,3-butadiene.
  • dihalogenated alkanes such as dichloroethane, dibromoethane, methylene chloride, dibromomethane, dichloropropane, and dibromoprop
  • the coupled block copolymer of this invention is suitable for use in hot-melt type pressure-sensitive adhesives.
  • the content of the alkenyl aromatic compound in the coupled block copolymer is preferably 3 to 50% by weight, more preferably 5 to 40% by weight in view of the balance among adhesion-holdability, die-cuttability and initial adhesive strength of said adhesives.
  • the coupled block copolymer of this invention when used in pressure-sensitive adhesive compositions, may contain block copolymers other than those coupled with a tin compound, namely uncoupled block copolymers and/or block copolymers coupled with a not-tin type coupling agent.
  • the content of these other block copolymers is preferably from 0 to 80% by weight, more preferably 50% by weight or less based on the total block copolymers.
  • the weight ratio of the coupled alkenyl aromatic compound-conjugated diene block copolymer and the other block copolymer is preferably from 30:70 to 100:0.
  • Said other block copolymers include those represented by the following general formulas:
  • A is a block of a polymer of an alkenyl aromatic compound or a block of a copolymer of an alkenyl aromatic compound (main component) and another monomer such as a conjugated diene compound or the like;
  • B is a block of a polymer of a conjugated diene compound or a block of a copolymer of a conjugated diene compound (main component) and another monomer such as an alkenyl aromatic compound or the like;
  • Z is the residue of a non-tin type coupling agent;
  • m is an integer of 1 or more; and
  • n'' is an integer of 1 to 6 corresponding to the functionality of Z.
  • the block copolymers represented by the general formulas (3), (4) and (6) are particularly preferred.
  • the block copolymer represented by the general formula (3) can be produced as follows.
  • an alkenyl aromatic compound is firstly polymerized using an organolithium compound as a polymerization initiator. After the polymerization has been substantially completed, a conjugated diene compound is added and polymerized. Then, an alkenyl aromatic compound same as or different from the above one is added and polymerized.
  • the block copolymers represented by the general formulas (4) and (5) can be produced in accordance with the process mentioned above or in accordance with a process for producing the block copolymer represented by the general formula (6) which is described below.
  • an alkenyl aromatic compound is firstly polymerized and then a conjugated diene compound is added and polymerized in the same manner as in the production of the block copolymer of the general formula (3); thereafter, a coupling agent having at least two but at most 6 functional groups is added to couple the polymers formed.
  • the organic acid includes aliphtic monocarboxylic acids such as stearic acid, oleic acid, and palmitic acid; aliphtic dicarboxylic acids such as maleic acid, and fumaric acid; aromatic monocarboxylic acids such as benzoic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; resin acids such as abietic acid, neoabietic acid, dihydroabietic acid, tetrahydroabietic acid, ⁇ -pimaric acid, iso- ⁇ -pimaric acid, dihydropimaric acid, and levopimaric acid. These organic acids can be used alone or in admixture of two or more.
  • the amount of the organic acid used is 20 parts by weight or less, preferably 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, and most preferably 0.2 to 10 parts by weight, per 100 parts by weight of the above-mentioned block copolymer mixture.
  • the amount of the organic acid is outside the above range, the resulting pressure-sensitive adhesive has a poor balance between initial adhesive strength and adhesion-holdability.
  • the initial adhesive strength can be improved by addition of one of the above-mentioned organic acids.
  • the tackifier includes a rosin type resin, a polyterpene type resin, a synthetic polyterpene type resin, an alicyclic hydrocarbon resin, a coumarone type resin, a phenol type resin, a terpene-phenol type resin, an aromatic hydrocarbon resin, and an aliphatic hydrocarbon resin,.
  • the rosin type resin, the polyterpene type resin and the alicyclic hydrocarbon resin are particularly preferred.
  • These tackifiers can be used alone or in admixture of two or more.
  • the amount of the tackifier used is 20 to 200 parts by weight, preferably 50 to 150 parts by weight, and more preferably 70 to 130 parts by weight, per 100 parts by weight of the block copolymer mixture. When the amount of the tackifier is outside the above range, the resulting pressure-sensitive adhesive is insufficient in initial adhesive strength and adhesion-holdability.
  • the pressure-sensitive adhesive composition can further contain a softener.
  • the softener includes, for examples, naphthenic, paraffinic and aromatic process oils and these can be used alone or in admixture of two or more.
  • the amount of the softener used is 0 to 100 parts by weight, preferably 20 to 70 parts by weight, per 100 parts by weight of the block copolymer mixture. When the amount of the softener exceeds 100 parts by weight, the softener bleeds onto the surface of the pressure-sensitive adhesive composition with the lapse of time, which is undesirable.
  • the pressure-sensitive adhesive composition of this invention may further contain, if necessary, a stabilizer (e.g., an anti-oxidant, an ultraviolet absorber), an inorganic filler (e.g., calcium carbonate, talc, clay, titanium oxide, silica, magnesium carbonate, carbon black), a coloring agent.
  • a stabilizer e.g., an anti-oxidant, an ultraviolet absorber
  • an inorganic filler e.g., calcium carbonate, talc, clay, titanium oxide, silica, magnesium carbonate, carbon black
  • a coloring agent e.g., calcium carbonate, talc, clay, titanium oxide, silica, magnesium carbonate, carbon black
  • the pressure-sensitive adhesive composition according to this invention exhibits the largest economical effect when it is heat-melted, mixed uniformly and coated as it is to form an adhesive layer.
  • this composition can also be coated after being diluted with an ordinary solvent or after being emulsified.
  • the pressure-sensitive adhesive composition of this invention obtained as above is coated on a substrate to form an adhesive layer. Therefore, this composition is effectively used in such applications as pressure-sensitive adhesive tapes, labels, backing pastes for fixing light weight, shaped plastic articles and backing pastes for fixing carpets. Further, the composition is effective as an adhesive layer material for pressure-sensitive adhesive tapes and labels used for frozen food or used in cold districts.
  • the coupled block copolymer of this invention has other extensive applications. It can preferably be used in such applications as, for example, injection moldings (e.g., footwears, containers), flow moldings (e.g., toys, household articles) and compression moldings (e.g., packings, sheets, plates). Further, the coupled block copolymer of this invention can be used for altering the physical properties of other rubbers such as SBR, NBR and the like or plastics such as a polystyrene and the like, by incorporating it into said other rubbers or plastics.
  • injection moldings e.g., footwears, containers
  • flow moldings e.g., toys, household articles
  • compression moldings e.g., packings, sheets, plates.
  • the coupled block copolymer of this invention can be used for altering the physical properties of other rubbers such as SBR, NBR and the like or plastics such as a polystyrene and the like, by incorporating it into said other rubbers or plastics.
  • the coupled block copolymer of this invention is utilized as an improver of, for example, impact resistance for crepe type sponges (when mixed with rubbers) or for general-purpose polystyrenes (when mixed with plastics).
  • the coupled block copolymer of this invention can be mixed with asphalts for an improvement of their low temperature resitance.
  • the polymerization temperature was controlled at 70°C. After completion of the last polymerization, to the polymerization mixture was added 2,6-di-tert-butyl-p-cresol and then cyclohexane was removed by heating to obtain a block copolymer.
  • the compound shown in Table 1 was prepared.
  • the compound was dissolved in a mixed solvent consisting of equal volumes of methylene chloride and toluene; the resulting solution was coated in a thickness of 30 to 35 ⁇ m on a polyester film of 50 ⁇ m in thickness; and the coated polyester film was dried for 20 min at 100°C to obtain a pressure-sensitive adhesive tape.
  • the tape was measured for adhesion characteristics. The measurement results are shown in Table 2.
  • Block copolymer 100 Synthetic polyterpene resin (Quintone U-185, brand name of Nippon Zeon Co., Ltd.) 100 Process Oil of naphthene type (Diana Process Oil NM-280, brand name of Idemitsu Kosan) 20 Anti-oxidant of phenol type (Nocrack NS-6, brand name of Ohuchi Shinko Kagaku) 3 Stearic acid 2
  • Example 9 The structure and physical properties of each coupled block copolymer obtained are shown in Table 2.
  • the block B was obtained by adding a mixture of styrene and isoprene in three portions and, after each addition, substantially 100% polymerizing each of the added portions, and had three tapered bloks in which the content of bound styrene increased gradually.
  • the block copolymers of Examples 1 to 8, as compared with those of Comparative Examples 1 to 5, are superior in balance of initial adhesive strength, peeling strength and die-cuttability and are less liable to cause blocking phenomenon.
  • the block copolymer obtained was subjected to evaluation of adhesion characteristics in the form of the same compound as in Example 1. The results are shown in Table 2.
  • Block copolymers A2 and A3 were produced by repeating the same procedure as used in the production of A1, except that different monomer amounts, different coupling agent amounts and different polymerization periods were used. The details of the block copolymers A2 and A3 are shown in Table 3.
  • a block copolymer A5 was produced by repeating the same procedure as in the production of the block copolymer A4, except that different monomer amounts, a different coupling agent amount and different polymerization periods were used.
  • a block copolymer B3 was produced by repeating the same procedure as in the production of B2, except that different monomer amounts and different polymerization periods were used.
  • the compound with the compounding recipe shown in Table 5 was placed in a mixing tank heated to 100°C. The same was stirred for 60 min to obtain a pressure-sensitive adhesive composition having a uniformity and a smooth fluidity.
  • Each of the pressure-sensitive adhesive compositions obtained was taken out in a molten state and coated on a substrate made of a polyester film by means of an applicator so that the coating layer had a thickness of 30 ⁇ , whereby various pressure-sensitive adhesive tape samples were prepared. On each of these pressure-sensitive adhesive tape samples, initial adhesive strength, peeling strength, adhesion-holdability and die-cuttability were measured. The results are shown in Table 5.
  • Example 6 Using styrene, isoprene, tetrahydrofuran, cyclohexane, and coupling agents in the amounts shown in Table 6, polymerization was conducted in the same manner as in Example 1 to obtain various block copolymers. The structures and physical properties of these block copolymers are shown in Table 6. Using the block copolymers, there were prepared the compositions shown in Table 7. Each of them was placed in a mixing tank heated to 160°C and stirred for 60 min, whereby various pressure-sensitive adhesive compositions having a uniformity and a smooth fluidity were obtained.
  • Each of these pressure-sensitive adhesive compositions was taken out in a molten state and coated on a polyester film by means of an applicator in a thickness of 30 ⁇ to prepare a pressure-sensitive adhesive tape.
  • These pressure-sensitive adhesive tapes were subjected to measurement of a low temperature tack, a peeling strength, an adhesion-holdability at high temperatures and a sealability for corrugated board. The results are shown in Table 7. The above measurements were made in accordance with the following test methods:
  • Two corrugated boards each having a size of 40 mm x 40 mm were cut off from a commercially available corrugated box. The two boards were contacted at one end of each. On this border, the two boards were pressure-bonded with a tape sample of 10 mm in width and 40 mm in length by applying a load of a 2 kg roll 10 times under the environmental conditions of 25°C and 65% RH. The resulting corrugated boards adhered were placed on a flap test apparatus shown in the accompanying drawing, and a load (200 g x 2) was applied and the time required until the load fell down was measured. Each measurement value is an average of the values of five samples.

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  • Organic Chemistry (AREA)
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  • Polymers & Plastics (AREA)
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Claims (14)

  1. Composition d'adhésif adhérant par pression, comprenant :
    (a) 100 parties en poids d'un copolymère séquencé contenant au moins 20% en poids d'un composé alcényle aromatique et d'un copolymère séquencé de diène conjugué couplés ensemble présentant une teneur totale en composé alcényle aromatique lié de 3 à 70% en poids, ayant une masse moléculaire moyenne en poids de 10.000 à 1.000.000 et répondant à la formule générale :



            [(A-B)m]n X et/ou




            [(A-B-A')m]n X



    dans lesquelles A et A', qui peuvent être identiques ou différents représentent chacun une séquence d'un polymère d'un composé alcényle aromatique, ayant une masse moléculaire moyenne en poids comprise entre 3000 et 200.000 ;
    B représente une séquence d'un polymère diène conjugué ou une séquence d'un copolymère diène conjugué/composé alcényle aromatique, présentant une proportion en diène conjugué d'au moins 50% en poids, ladite séquence ayant une masse moléculaire moyenne en poids de 7000 à 700.000 ;
    X représente le reste d'un agent de couplage contenant de l'étain ou un mélange du reste d'un agent de couplage contenant de l'étain et du reste d'un agent de couplage ne contenant pas de l'étain, le copolymère séquencé couplé contenant au moins 20% en poids d'un copolymère séquencé alcényle aromatique/diène conjugué couplé au composé d'étain;
    m est un nombre entier de 1 ou plus ; et n est un nombre entier de 2 à 6 correspondant à la fonctionnalité de X ;
    (b) de 20 à 200 parties en poids d'un agent d'adhésivité ;
    (c) de 0 à 20 parties en poids d'un acide organique ; et
    (d) de 0 à 100 parties en poids d'un adoucissant.
  2. Composition d'adhésif adhérant par pression selon la revendication 1, dans laquelle le copolymère séquencé comprend de 20 à 100% en poids d'un copolymère séquencé couplé de composé alcényle aromatique et de diène conjugué répondant à la formule générale :



            [(A-B)m]n X et/ou




            [(A-B-A')m]n X



    et de 80 à 0% en poids d'un autre copolymère séquence.
  3. Composition d'adhésif adhérant par pression selon la revendication 2, dans laquelle le rapport pondéral du copolymère séquencé composé couplé alcényle aromatique/diène conjugué et de l'autre copolymère séquencé est compris entre 30:70 et 100:0.
  4. Composition d'adhésif adhérant par pression selon les revendications 1 à 3, dans laquelle ledit autre copolymère séquencé est au moins un copolymère séquencé de formule :



            (A-B)-mA,   (A-B)-m,




            (B-A)-mB,   [(A-B)m]n'' Z et




            [(A-B-A)-m]n'' Z



    dans laquelle A représente une séquence d'un polymère de composé alcényle aromatique ou une séquence d'un copolymère de composé alcényle aromatique (composant principal) et d'un diène conjugué ; B représente une séquence d'un polymère de composé de diène conjugué ou une séquene d'un copolymère d'un diène conjugué (composant principal) et d'un composé alcényle aromatique ; Z représente le reste d'un agent de couplage ne contenant pas d'étain ; m est un nombre entier de 1 ou plus ; et n'' est un nombre entier de 1 à 6 qui correspond à la fonctionnalité de Z.
  5. Composition d'adhésif adhérant par pression selon la revendication 4, dans laquelle ledit autre copolymère séquencé est un copolymère séquencé de formule (A-B)m.
  6. Composition d'adhésif adhérant par pression selon l'une quelconque des revendications 1 à 5, dans laquelle la quantité de l'agent d'adhésivité est de 50 à 150 parties en poids.
  7. Composition d'adhésif adhérant par pression selon l'une quelconque des revendications 1 à 6, dans laquelle la quantité d'acide organique est de 0,01 à 20 parties en poids.
  8. Composition d'adhésif adhérant par pression selon l'une quelconque des revendications 1 à 7, dans laquelle la quantité d'adoucissant est de 20 à 70 parties en poids.
  9. Copolymère séquencé d'un composé alcényle aromatique couplé et de diène conjugué servant à la préparation d'un adhésif adhérant par pression tel que revendiqué dans l'une quelconque des revendications 1 à 8, présentant une teneur totale en composé alcényle aromatique combiné de 3 à 70% en poids, ayant une masse moléculaire en poids de 10.000 à 1.000.000 et répondant à la formule générale:



            [(A-B)m]n X et/ou




            [(A-B-A')m]n X



    dans laquelle A et A', qui sont identiques ou différents, représentent chacun une séquence d'un copolymère de composé alcényle aromatique ayant une masse moléculaire moyenne en poids de 3000 à 200.000 ;
    B représente une séquence d'un polymère de diène conjugué ou une séquence d'un copolymère diène conjugué/composé alcényle aromatique, contenant une proportion de diène conjugué d'au moins 50% en poids, ladite séquence présentant une masse moléculaire moyenne en poids de 7000 à 700.000 ;
    X représente le reste d'un agent de couplage contenant de l'étain ou un mélange du reste d'un agent de couplage contenant de l'étain et du reste d'un agent de couplage ne contenant pas d'étain, le copolymère séquencé couplé contenant au moins 20% en poids d'un copolymère séquencé d'un composé alcényle aromatique couplé avec un composé d'étain et de diène conjugué ; et X représente le reste d'au moins un agent de couplage choisi parmi le chlorure stanneux, le chlorure stannique, le bromure stanneux, le bromure stannique, l'iodure stanneux, l'iodure stannique, le fluorure stanneux, le fluorure stannique, le trichlorure de méthylétain, le trichlorure de butylétain ou le dichlorure de dibutylétain ;
    m est un nombre entier de 1 ou plus ; et
    n est un nombre entier de 2 à 6 qui correspond à la fonctionnalité de X.
  10. Copolymère selon la revendication 9, dans lequel la teneur totale en composé alcényle aromatique combiné est de 5 à 50% en poids.
  11. Copolymère selon la revendication 9, dont la masse moléculaire est de 50.000 à 700.000.
  12. Copolymère selon l'une quelconque des revendications 9 à 11, dans lequel la séquence A présente une masse moléculaire de 5000 à 50000 et la séquence B présente une masse moléculaire de 10.000 à 200.000.
  13. Copolymère selon l'une quelconque des revendications 9 à 12, dans lequel la séquence B comporte de 2 à 10 séquences inclinées dans lesquelles la teneur en composé alcényle aromatique combiné augmente progressivement.
  14. Copolymère selon l'une quelconque des revendications 9 à 13, dans lequel X contient de 20 à 100 moles% de résidu d'un agent de couplage contenant de l'étain.
EP85305240A 1984-07-23 1985-07-23 Adhésif sensible à la pression et copolymères pour le préparer Expired - Lifetime EP0171225B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP59152232A JPS61171714A (ja) 1984-07-23 1984-07-23 粘着剤組成物
JP152232/84 1984-07-23

Publications (2)

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EP0171225A1 EP0171225A1 (fr) 1986-02-12
EP0171225B1 true EP0171225B1 (fr) 1992-03-25

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EP (1) EP0171225B1 (fr)
JP (1) JPS61171714A (fr)
DE (1) DE3585710D1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090094442A (ko) * 2006-12-07 2009-09-07 쓰리엠 이노베이티브 프로퍼티즈 컴파니 다수의 점착성 부여제를 포함하는 블록 공중합체 블렌드 접착제

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0686586B2 (ja) * 1985-04-05 1994-11-02 日東電工株式会社 感圧性接着剤組成物
JPS61291610A (ja) * 1985-06-18 1986-12-22 Japan Synthetic Rubber Co Ltd ブロツク共重合体およびその組成物
IT1198213B (it) * 1986-12-01 1988-12-21 Enichem Elastomers Copolimeri a blocchi radiali e ramificati,composizioni che li contengono,loro preparazione e loro uso in composizioni bituminose
US5272214A (en) * 1986-12-01 1993-12-21 Enichem Elastomeri S.P.A. Radial and branched block copolymers, compositions which contain them, their preparation and their use in bituminous compositions
JPH0788459B2 (ja) * 1987-06-30 1995-09-27 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー ブロック共重合体組成物
JP2701268B2 (ja) * 1987-09-22 1998-01-21 日本合成ゴム株式会社 ブロック共重合体組成物
EP0394229A1 (fr) * 1988-03-24 1990-10-31 Shell Internationale Researchmaatschappij B.V. Composition de copolymere bloc
BE1001592A3 (fr) * 1988-04-27 1989-12-12 Fina Research Procede de preparation de copolymeres sequences.
US5399627A (en) * 1989-08-11 1995-03-21 The Dow Chemical Company Radial styrene-isoprene-butadiene multi-armed block copolymers and compositions and articles containing block copolymers
EP0425027B1 (fr) * 1989-10-26 1995-06-14 Shell Internationale Researchmaatschappij B.V. Polymère en étaile, sa préparation et les compositions lubrifiantes contenant celui-ci
GB2254333B (en) * 1989-11-01 1994-03-16 Swift Adhesives Ltd Crosslinkable polymers
GB8924619D0 (en) * 1989-11-01 1989-12-20 Swift Adhesives Ltd Crosslinkable polymers
US5118762A (en) * 1990-04-11 1992-06-02 Shell Oil Company Styrene-isoprene-styrene block copolymer composition for low viscosity low temperature hot melt adhesives
US5194500A (en) * 1992-02-28 1993-03-16 Shell Oil Company Styrene-isoprene three-armed high load bearing capacity block copolymer composition for adhesives
US5183705A (en) * 1992-02-28 1993-02-02 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive composition having high shear strength
US5563204A (en) * 1993-01-08 1996-10-08 The Dow Chemical Company High-strength films of block copolymer latices
JPH08505426A (ja) * 1993-01-08 1996-06-11 ザ ダウ ケミカル カンパニー ブロックコポリマーラテックスの高強度フィルム
US5578674A (en) * 1993-01-08 1996-11-26 The Dow Chemical Company High-strength films of block copolymer latices
US5905097A (en) * 1993-01-08 1999-05-18 The Dow Chemical Company High-strength breathable films of block copolymer lattices
JP3476920B2 (ja) * 1994-08-18 2003-12-10 日本エヌエスシー株式会社 衛生材料用ホットメルト接着剤組成物
JPH0860122A (ja) * 1994-08-18 1996-03-05 Kanebo Nsc Ltd ホットメルト接着剤組成物
US5567760A (en) * 1994-11-15 1996-10-22 The Dow Chemical Company Films from aqueous dispersions of block copolymers having hydrogenated conjugated diene block
GB2322133A (en) * 1997-02-14 1998-08-19 Goodyear Tire & Rubber Asymmetrical tin-coupled rubbery polymers
JP6665492B2 (ja) * 2015-11-06 2020-03-13 Dic株式会社 粘着剤、粘着テープ及び粘着テープの製造方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL288289A (fr) * 1962-01-29
US3778490A (en) * 1969-04-23 1973-12-11 Phillips Petroleum Co Polar compound adjuvants for improved block polymers prepared with primary hydrocarbyllithium initiators
GB1527226A (en) * 1974-12-06 1978-10-04 Shell Int Research Preparation of a non-linear elastomeric copolymer
US4080348A (en) * 1976-05-18 1978-03-21 Johnson & Johnson Tacky adhesive
JPS5679147A (en) * 1979-11-30 1981-06-29 Asahi Chem Ind Co Ltd Impact-resistant resin composition
EP0134909B1 (fr) * 1980-12-17 1988-06-29 Japan Synthetic Rubber Co., Ltd. Copolymères butadiène-styrène

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090094442A (ko) * 2006-12-07 2009-09-07 쓰리엠 이노베이티브 프로퍼티즈 컴파니 다수의 점착성 부여제를 포함하는 블록 공중합체 블렌드 접착제

Also Published As

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EP0171225A1 (fr) 1986-02-12
DE3585710D1 (de) 1992-04-30
JPH037229B2 (fr) 1991-02-01
JPS61171714A (ja) 1986-08-02

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